Comparison of profile tailing in SIMS analyses of various impurities in silicon using nitrogen,oxygen, and neon ion beams at near-normal incidence

We have performed a systematic SIMS study into the effect of (i) the chemical nature and (ii) the energy of the primary ions on the decay length which characterizes the exponential fall-off of impurity sputter profiles. The samples consisted of low resistivity, p-type Si covered with thin metallic overlayers. Bombardment was carried out at 2° off normal. Aspect (i) was investigated for tracers of Cu and Ga using N ₂ ⁺ , O ₂ ⁺ , and Ne⁺ primary ions at an energy of 5 keV/atom. The effect of the beam energy, aspect (ii), was studied for eight different tracer species and N ₂ ⁺ primary ions at energies between 2 and 5 keV/atom. In the case of Ga, was found to be shorter with N ₂ ⁺ or O ₂ ⁺ primary ions (=7.0 and 7.5 nm, respectively) than with Ne⁺ (=12 nm). This effect is attributed to beam induced formation of Si₃N₄ or SiO₂ layers, whereby the effective width of the internal distribution of intermixed Ga impurities in the Si subsystem is reduced significantly. In contrast to Ga, the decay length for Cu is smallest under bombardment with Ne⁺ (=16 nm), quite large with N ₂ ⁺ (26 nm) and extremely large with O ₂ ⁺ (2.2 m). Segregation of Cu atoms at the Si₃N₄/Si and the SiO₂/Si interface, respectively, is responsible for this depressed impurity removal rate. Within experimental accuracy the observed variation of the decay length with N ₂ ⁺ energy E [keV/atom] can be written in the form =kE ^p, where k and p are element specific parameters which range from k=1.2 nm for Pb to 10 nm for Cu and from p=0.6 for Cu and Ag to 1.0 for Pb. The results are discussed with reference to conceivable shapes of the distribution of intermixed impurity atoms.On leave from NTT Applied Electronics Laboratories, 3-9-11, Midori-cho, Musashino-shi, Tokyo 180, Japan     

Energy deposition,reflection and sputtering in hyperthermal rare-gas→Cu bombardment

Using molecular-dynamics simulation, we study the scattering and penetration of normally incident hyperthermal (5–400 eV) Ne, Ar, and Xe atoms off a Cu crystal. We find that between 80% and 98% of the incident energy is deposited in the solid; the fraction depends primarily on the projectile mass, and — for not too low energies — only slightly on the bombarding energy. At low energy, the major part of the non-deposited energy is carried away by the reflected projectile. At energies above the sputter threshold, an increasingly important contribution of between 2% and 6% of the incident energy is carried away by sputtered particles. These results compare well with experiment. Electronic inelastic losses show only little influence on this behaviour. We demonstrate that the inclusion of a realistic attractive interaction between the projectile and the target atoms influences the energy deposition considerably at energies below around 100 eV.     

Oxidation of cobalt at room temperature,studied by combined static SIMS,static AES,XPS and work function investigations

The room temperature oxidation of cobalt has been found to proceed in two distinct steps, the first of which (at 0–20 L oxygen exposure) leads to oxygen chemisorption without formation of oxide-like bonds, the second step (at > 20 L) consists of the formation and in-depth growth of a surface oxide. Both stages can be distinguished by their characteristic secondary ion emission, in particular by the energy distribution of the positive secondary ions, which changes with oxygen coverage, and by their characteristic electron spectroscopic signals, in particular the occurrence of CoM₂₃VL(O)₂₃ and CoM₂₃VL(O)₁ cross transitions in the second stage, which have been observed for the first time in surface oxide layers in the monolayer range.     

Low energy selfsputtering yields of nickel

The selfsputtering yield of nickel has been measured by the mass change method for normal incidence in the energy region from 75eV–3.0keV. In this energy region the yield varies from 0.07–3.0atmos/ion. The results are discussed in view of their importance to the plasma-wall interaction in fusion devices.     

The effect of target texture and topography on the spatial distribution of material sputtered from tungsten

The spatial distributions of sputtered particles have been investigated both experimentally and by computer simulation using the TRIM.SP code for 30 keV argon-ion bombardment of tungsten in a wide range of primary-ion incidence angles (0°–80°). Two sets of the targets were used. One of them was prepared from fine-grained polycrystalline ingot, another one from rolled sheet W. It was found that the experimental results for these targets were different. For rolled tungsten a typical Wehner-spot picture, although smeared, is observed. For fine-grained tungsten the sputtered particle spatial distributions are practically cupola-shaped. Some differences between the experimental results and computer-simulation data can be attributed to the effect of surface topography either initial or developed during the ion bombardment.     

Studies of CdTe surfaces with secondary ion mass spectrometry,rutherford backscattering and ellipsometry

The composition and the stability of chemically etched, mechanically polished and oxidized surfaces of single crystals of cadmium-telluride were studied by secondary ion mass spectroscopy (SIMS), Rutherford backscattering (RBS) and ellipsometry. CdTe surfaces etched using a solution of bromine in methanol were found to be enriched in cadmium but a film, identified to be an oxide of tellurium, was observed to grow on it at room temperature and in air. The thickness of this film increased over long periods of timet linearly versus lnt. Mechanically polished samples and also chemically etched surfaces which were oxidized in a solution of hydrogen peroxide in amoniac were found to be stable.     

AES and XPS investigations of the surface layers of porous silicon with Fe,Co, and Ni embedded pores

A Composite material of porous silicon with pore embedded d-metals por-Si(Me) can be used for fabricating memory cells. Por-Si layers have been produced by electrochemical etching of n-type silicon (100) according to the conventional process. Fe, Co, and Ni galvanic deposition in por-Si has been performed using aqueous solutions of corresponding sulfate salts. The Auger profiles of the obtained por-Si(Fe), por-Si(Co), por-Si(Ni) nanocomposites have shown that its surface layers (up to 40 nm thick) contained about 10% Fe and no more than 1% Co and Ni. These facts confirm data that Co and Ni, unlike Fe, penetrate deep into the silicon pores. The value of the magnetic moment for the nanocrystalline Ni atom incorporated into the por-Si(Ni) has been estimated based on the dependence of the relative intensity of the maxima for the 3s multiplet splitting of the X-ray phase spectra on the number of uncoupled d-electrons in systems with 3d metals. The obtained value ∼2.4 μB exceeds the atomic magnetic moment in bulk metallic Ni.     

Ion mixing in Al,Si, and their oxides

The redistribution of thin metallic markers due to ion irradiation was studied by backscattering spectrometry in Al, Al₂O₃, Si, and SiO₂. Marker species were selected for their similar masses and different chemical reactivities with the host media and included Ti, Fe, W, Pt, and Au. It was found that the marker signals are Gaussian and that the variance ² of the marker atom distributions increases linearly with the dose of the irradiation, is insensitive to the temperature of irradiation in the range of 80–300 K, and depends linearly on the nuclear stopping power of the incident ions. The absolute values of ² for Ti, Fe, W, Pt, and Au markers in Al and Al₂O₃, W, and Pt in SiO₂ and W in Si is, within±50 %, of 6.5×10³Å² for 300 keV, 8×10¹⁵ Xe ions/cm². These observations suggest that collisional cascade mixing is a dominant mechanism in this type of impurity-matrix combinations. Only Au and Pt in Si mix at a larger rate: ² for Pt is about 3 and for Au about 5 times larger than ² for all other markers. Lower threshold displacement energies and/or the contribution of processes other than cascade mixing are possible considered reasons. In polycrystalline Al, a rapid migration of Au and Pt atoms throughout the Al layer, similar to grain boundary diffusion, is observed.     

XPS and AES investigations of hard magnetic Nd-Fe-B films

Nd-Fe-B is a promising material system for the preparation of thin films with good hard magnetic properties. One problem of this material class is the sensitivity against oxidation, resulting in a degradation of the magnetic properties. Using XPS depth profiling in combination with peak-shape analysis it is shown that already after several hours oxygen can diffuse deep into the thin laser-deposited films and that Nd is mainly responsible for the oxidation. Local element analysis with AES revealed boron inhomogeneities from droplet formation during laser deposition. These problems can be solved by using a capping Cr layer and an FeB target for thin film preparation, respectively.     

Sputtering of multicomponent materials

The nonlinear balance equation, describing the evolution of concentration profiles for a multicomponent target under the action of ion bombardment as a function of the depth inside the target and the incident ion fluence, was solved numerically. The quantities of interest have been calculated with reference to a binary system showing that the balance equation is consistent with the correct stoichiometry for the sputtering yield ratio in the stationary state.     

Collision cascade evolution in media with energy independent scattering: spatial,energy, and angular distribution

The evolution of an ion induced collision cascade in a solid medium is studied by means of a DPl-approximation to the linear transport equation. Infinite medium and half space geometries are considered. Special attention is given to the effect of the anisotropy of the energy independent scattering cross section. We present results on the spatial distribution of particles moving at different energies, and the energy and angle distribution at the target surface. The spatial distributions are found to obey simple scaling laws; the energy and angular distributions are independent of the form of the scattering cross section, unless it is very strongly forward peaked.     

Energy spectra of atoms sputtered by KeV light-ion bombardment

A calculation has been made for the sputtering of heavy targets by KeV light-ion bombardment. The calculation is based both on linear transport theory and on the assumption that only primary recoiling atoms are candidates for the sputtering process. The energy spectra calculation predicts the experimentally observed peak shift towards lower velocities than those obtained by standard linear cascade theory.     

Experimental and theoretical investigations into the origin of cross-contamination effects observed in a quadrupole-based SIMS instrument

The minimum-detection limits achievable in SIMS analyses are often determined by transport of material from surrounding surfaces to the bombarded sample. This cross-contamination (or memory) effect was studied in great detail, both experimentally and theoretically. The measurements were performed using a quadrupole-based ion microprobe operated at a secondary-ion extraction voltage of less than 200 V (primary ions mostly 8keV O ₂ ⁺ ). It was found that the flux of particles liberated from surrounding surfaces consists of neutrals as well as positive and negative ions. Contaminant species condensing on the bombarded sample could be discriminated from other backsputtered species through differences in their apparent energy spectra and by other means. The apparent concentration due to material deposited on the sample surface was directly proportional to the bombarded area. For an area of 1 mm² the maximum apparent concentration of Si in GaAs amounted to 5 × 10¹⁶atoms/cm³. The rate of contamination decreased strongly with increasing spacing between the bombarded sample and the collector. The intensities of backsputtered ions and neutrals increased strongly with increasing mass of the target atoms (factor of 10 to 50 due to a change from carbon to gold). The effect of the primary ion mass (O ₂ ⁺ , Ne⁺, and Xe⁺) and energy (5–10keV) was comparatively small. During prolonged bombardment of one particular target material, the rate of contamination due to species not contained in the sample decreased exponentially with increasing fluence. In order to explain the experimental results a model is presented in which the backsputtering effect is attributed to bombardment of surrounding walls by high-energy particles reflected or sputtered from the analysed sample. The level of sample contamination is described by a formula which contains only measurable quantities. Cross-contamination efficiencies are worked out in detail using calculated energy spectra of sputtered and reflected particles in combination with the energy dependence of the sputtering yield of the assumed wall material. The experimental findings are shown to be good agreement with the essential predictions of the model.     

Combined XPS and SIMS study of amino acid overlayers

Factors influencing the SIMS fragmentation patterns are studied for three simple amino acids-glycine, α-alanine, and serine-deposited onto Ag substrates from aqueous solution. Secondary ion emissions are measured for 1 keV Ar⁺ ions incident at 70° from sample normal as a function of substrate preparation and solution concentration. Studies by XPS and X-ray induced AES prior to SIMS analysis show that the amino acids adsorb in a film on the Ag surface and that the film thickness increases with solution concentration. In addition, considerable amounts of amino acid can be deposited on the surface from a water film retained during extraction from a concentrated solution. On acid etched samples, positive ion fragments of mass AgM, Ag(M ? 45), Ag, M + 1, and M ? 45 are observed, where M is the molecular, weight of the parent amino acid. With the exception of the (M + 1)⁺ fragment, these peak intensities behaved similarly for the different surface concentrations. When the adsorbed film grows too thick, the positive molecular ion emissions drop considerably; this substantiates the need for proximity between the Ag substrate and the amino acid molecule.     

The determination of shadowing critical angles in impact collision ion scattering spectroscopy

Critical angles for shadowing in low-energy ion scattering spectroscopy are calculated in the momentum approximation for the Thomas-Fermi-Molière potential and the Ziegler-Biersack-Littmark potential. In the relevant parameter range the results can be fitted by a formula containing five constants depending on the potential only. For a fixed projectile-target combination at a given energy the distance dependence of the critical angle is described by a simple power law. The comparison of the calculated results with experimental data shows that the inclusion of the effect of thermal vibrations on the critical angles improves the agreement between calculations and experiment significantly.     

AES investigations of Ar+ ion retention in Si during Ar sputtering

Argon retention in silicon has been studied by AES in the energy range between 1 and 15 keV at bombardment fluences up to ∼10¹⁸ ions/cm². AES data of implanted argon in silicon near the surface region, as obtained during sputtering, can be interpreted qualitatively by a simple model of ion collection. Discrepancies between calculated and measured saturation values of collected argon ions indicate that during implantation at high fluences addition surface effects become important and that the simple model of ion collection has to account for this. Quantitative AES correlated with RBS indicates pronounced concentration gradients of argon in silicon near surface regions.     

XPS analysis of palladium oxide layers and particles

The thermal reduction of both oxidised palladium foil and SiO₂/Si(100) supported palladium oxide particles, ranging in size fro 3.5 to 13 nm, was investigated with XPS. Equations were derived for the XPS intensities, measured at normal emission angles, of the particles which consisted of a metallic core and an oxidic skin. By applying these equations on the spectra measured after each reduction step, the particle size and the size of the metallic core were calculated. Measurements on palladium foil showed that the oxide layer thickness decreases linearly with the reduction time up to the last monolayer oxide. The reduction rate of the surface oxide is about eight times lower than the reduction rate of the bulk oxide. The growth of the metallic core in palladium oxide particles appeared to be linearly proportional to the surface area. The reduction rate of the smallest particles was comparable to the reduction rate of the surface oxide of the palladium foil. The larger particles behave identical to the palladium foil.     

Analysis of temperature and enhanced diffusion effects in sputtering of CrSi2

Previously reported experimental results on sputtering and enhanced diffusion processes in CrSi₂ during 100 keVXe⁺ bombardment at different temperatures have been quantitatively analyzed.The framework for the analysis is a simple theoretical model in which the Si atoms are considered mobile in a matrix of Cr atoms whose density is assumed constant and diffusivity is considered zero everywhere. Erosion velocity of the matrix (due to the sputtering of Cr atoms), sputtering and enhanced diffusion processes of Si atoms are taken into account in the mathematical model.In our analysis we show that the time evolution of the total number of sputtered atoms in binary solids cannot yield an unambigous conclusion as to the existence of preferential sputtering.Further, it is found that in the case of CrSi₂ the preferential sputtering of Si atoms depends on the suicide temperature.     

Analysis of solids by secondary ion and sputtered neutral mass spectrometry

A mass spectrometer is described, which allows the analysis of sputtered neutral and charged particles as well as of residual gas composition. This combined SIMS, SNMS, and RGA instrument consists of a scanning primary ion beam column, an electron impact ionizer, an electrostatic energy filter and an rf quadrupole mass analyzer.Various examples of surface and bulk analysis are presented which demonstrate the beneficial complementary features of these techniques. These are, in particular: a substantial reduction of the matrix effect and fewer complications with samples of low electrical conductivity in SNMS, and the possibility of measuring the depth distribution of gases included in small cavities in the solid in the SNMS/RGA mode. SIMS, on the other hand, allows in many cases higher detection sensitivities.EURATOM Association     

Effective temperature in the impact surface region during 100 keV Xe+ implantation of copper bars

The temperature evolution of a copper bar during 100 keV Xe ions implantation has been experimentally recorded. The thermal behaviour of the implanted bar is quantitatively described by a simple model calculation. It is shown that the experimental results may be reproduced by considering a radiative energy dissipation from hightemperature surface regions intersected by ion impact. The quantities characterizing these thermal-spike regions like average temperature and lifetime are consistent with earlier thermodynamical estimations reported in the current literature.